JP3421202B2 - Propylene polymerization method and propylene polymer obtained using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for polymerizing propylene. More specifically, it relates to a method for polymerizing propylene having extremely high activity and high stereoregularity.

[0002]

2. Description of the Related Art Conventionally, as a method for polymerizing propylene, a slurry method using hexane, heptane or the like as a solvent, a bulk method using propylene itself as a solvent, a gas phase method using an inert gas as a medium and the like are known. There is. In these methods, a polymer having high activity and high stereoregularity has come to be obtained by improving the performance of the catalyst used and improving the polymerization technique. However, in the slurry method, the concentration of the monomer in the reaction system in the solvent is low, and since the polymerization temperature is low, the polymerization activity is low, and there is a limit to increase it. Further, there is a problem that the solvent remains in the polymer to deteriorate the odor level of the polymer.

On the other hand, a bulk polymerization method in which polymerization is carried out in a liquid monomer is also carried out. However, in bulk polymerization, the polymerization temperature is low, so that the polymerization activity is not sufficient. There is a problem that a large amount of energy is required for reuse and the cost becomes high. Further, in the gas phase method, although there is no problem with the above-mentioned solvent or the like, there are problems in operation such that a lump polymer is easily generated. A polymerization method that solves these problems and realizes higher activity and higher productivity has been desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polymer having no problem of smell due to a solvent, formation of a lumpy polymer in a gas phase method, etc., extremely high polymerization activity, excellent productivity and high stereoregularity. It is to provide a manufacturing method.

[0005]

The present inventors have studied various polymerization methods in order to solve the above-mentioned problems, and as a result,
By polymerizing propylene under specific conditions, the inventors have found a method capable of providing a polymer having high polymerization stability and high activity and high stereoregulation, which has hitherto been unknown, and arrived at the present invention. That is, the present invention is a propylene-based monomer polymerization method, the polymerization temperature is higher than the critical temperature of the monomer component present in the polymerization system and is equal to or higher than the melting point of the polymer to be polymerized, The present invention provides a method for polymerizing propylene, characterized in that propylene is subjected to solventless polymerization under a condition that the polymerization pressure is higher than the critical pressure of the monomer component present in the polymerization system.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, polymerization is carried out at a temperature higher than the critical temperature of the monomer components present in the polymerization system and at a temperature not lower than the melting point of the polymer to be polymerized. That is, the polymerization temperature is
From the critical temperature of propylene to be subjected to polymerization, and when producing a copolymer, propylene and other comonomer components used (detailed below, ethylene, α-olefins having 4 or more carbon atoms, etc.) Higher than all critical temperatures of
In addition, the temperature range is not lower than the melting point of the polymer produced.

The polymerization pressure is higher than the critical pressure of the monomer components present in the polymerization system. In the present invention, the "melting point of the polymer" means the one obtained by polymerizing under the same conditions as the conditions actually carried out in advance and measuring the melting point of the resulting polymer by differential thermal analysis (DSC). Say.

When the polymerization temperature is lower than the critical temperature of the monomer component present in the polymerization system, the polymerization monomer is liquefied and the density of the monomer is increased, so that the advantages of the present invention can be enjoyed. In addition, the cost of separating and reusing the monomer increases. When it is lower than the melting point of the polymer, a propylene-based polymer having a wide molecular weight distribution, preferably having a Q value of 6 or more, which is the object of the present invention, cannot be obtained, which is not preferable.

Further, when the polymerization pressure is lower than the critical pressure of the monomer components present in the polymerization system, the supercritical phenomenon does not occur and high activity cannot be obtained. The polymerization temperature and the polymerization pressure vary depending on the conditions such as homopolymerization or copolymerization, or the presence or absence of a molecular weight regulator such as hydrogen. For example, in the case of producing a propylene homopolymer, the critical temperature of propylene is 91.4 The melting point of the resulting polymer is
Depending on the level of stereoregularity of the polymer obtained,
Generally, the temperature is 160 to 165 ° C, and therefore it is necessary to polymerize at 165 ° C or higher . The polymerization pressure is 4 because the critical pressure of propylene is 45.4 kg / cm ^2.
It is necessary to polymerize at a pressure higher than 5.4 kg / cm ² .

In the present invention, the polymerization temperature is 17
0 ° C to 250 ° C, polymerization pressure 50 to 300 kg / cm ²
Within the range , solventless polymerization is carried out. Solvent-free polymerization in the present invention refers to a method for slurry polymerization using a solvent, solution polymerization, different from the method of advancing the polymerization in a state where the catalyst and the polymer are dissolved or dispersed by adding a solvent to the polymerization system. The polymerization is performed in a composition containing a monomer as a main component. Polymerization typically proceeds in a monomer composition in a supercritical state. However, the coexistence of a small amount of solvent is not excluded, but rather it is a preferred embodiment that it is used as a diluent or a carrier when supplying catalyst components, additives, monomers and the like.

The polymerization apparatus that can be used in the present invention is not particularly limited as long as it can withstand the conditions such as temperature and pressure employed in the method of the present invention, and known polymerization apparatuses can be used. A stirring tank having an attached power generator, a loop type reaction tank in which the reaction system is circulated by a blower, and the like can be used.

In addition to propylene, as a monomer to be used in the polymerization in the present invention, a comonomer such as ethylene or α- having 4 or more carbon atoms and usually having 12 or less carbon atoms can be used.
Examples of the olefin include ethylene and butene-
1,4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-butene-1, and the like. The amount of comonomer is not particularly limited, but is 0.01 to 30% by weight, preferably 0.1 to 1
It is about 5% by weight.

The propylene-based polymer polymerized according to the method of the present invention preferably has an MFR of 5 to 1000 g / 10 minutes, and this MFR is measured according to ASTM D1238 (230). C., 2.16 kg load).

Further, the propylene polymer polymerized according to the method of the present invention preferably has a Q value of 6 or more. When the Q value is in this range, the moldability in terms of mechanical strength and the appearance of the molded article are excellent, and when it is too low, the moldability and the external appearance of the molded article tend to be poor. The Q value is Mw / Mn (M
w: weight average molecular weight measured by gel permeation chromatograph (GPC), Mn is number average molecular weight measured by GPC. ).

The catalyst used in the present invention may be any one as long as the effects of the present invention are recognized, but a Ziegler type catalyst, particularly a magnesium-supported type catalyst is used.
It is preferable because it has excellent activity at high temperatures. Specifically, it is composed of the following component (A) and component (B) or a combination of component (A), component (B) and component (C). Here, "composed of" means that the components used are only those listed above (that is, components (A) and (B), components (A), (B) and (C)). Does not mean that the coexistence of other components for the purpose is not excluded.

<Component A> Component (A) is a Ziegler-type catalyst solid component containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that other than the three listed components may contain a purposeful other element, and each of these elements exists as an intended compound. Good thing,
And that these elements may exist as bonded to each other. The solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45688 and 54-54
No. 3894, No. 54-31092, No. 54-394
No. 83, No. 54-94591, No. 54-118484
No. 54-131589, No. 55-75411,
55-90510, 55-90511, 55
-127405, 55-147507, 55-
155003, 56-18609, 56-70.
No. 005, No. 56-72001, No. 56-86905.
No. 56-90807, No. 56-155206,
57-3803, 57-34103, 57-
No. 92007, No. 57-12003, No. 58-53.
09, 58-5310, 58-5311, 58-8706, 58-27732, 58-3.
No. 2604, No. 58-32605, No. 58-6770
No. 3, No. 58-117206, No. 58-127708.
No. 58-183708 and No. 58-183709.
No. 59-149905, No. 59-149906, etc. are used.

Examples of the magnesium compound used as the magnesium source in the present invention include magnesium halide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. can give. Of these, preferred are magnesium halides, dialkoxymagnesiums, and alkoxymagnesium halides.

Further, the titanium compound as the titanium source is
General formula Ti (OR ')_4-qX_q (Where R'is hydrocarbon residue
A group, preferably having about 1 to 10 carbon atoms
X represents halogen and q represents a number of 0 ≦ q ≦ 4.
You ). As a specific example
Is TiCl_Four , TiBr_Four , Ti (OC₂ H_Five ) Cl
₃ , Ti (OC₂ H_Five )₂ Cl₂ , Ti (OC₂ H_Five )
₃ Cl, Ti (O-iC₃ H ₇ ) Cl₃ , Ti (O-n
C_Four H₉ ) Cl₃ , Ti (O-nC_Four H₉ )₂ Cl₂,
Ti (OC₂ H_Five ) Br₃ , Ti (OC₂ H_Five ) (OC
_Four H₉ )₂ Cl, Ti (O-nC_Four H₉ )₃ Cl, Ti
(OC₆ H_Five ) Cl₃ , Ti (O-iC_Four H ₉ )₂ C
l₂ , Ti (OC_Five H₁₁) C_l3 , Ti (OC₆ H₁₃)
C_l3 , Ti (OC₂H_Five )_Four , Ti (O-nC₃ H
₇ )_Four , Ti (O-nC_Four H₉ )_Four , Ti (O-iC_Four 
H₉ )_Four , Ti (O-nC₆ H₁₃)_Four , Ti (O-nC
₈ H₁₇)_Four , Ti [OCH₂ CH (C₂ H_Five ) C_Four H
₉ ]_Four And so on.

Further, TiX '_Four (Here, X'is a halogen
(Indicated by a
A thing can be used. As a specific example, TiCl_Four 
・ CH₃ COC₂ H_Five , TiCl_Four ・ CH₃ CO₂ C₂ 
H_Five , TiCl_Four ・ C₆ H_FiveNO₂ , TiCl_Four ・ CH₃
 COCl, TiCl_Four ・ C₆ H_Five COCl, TiCl_Four
 ・ C₆ H_Five CO₂ C₂ H_Five , TiCl_Four ・ ClCOC₂
 H_Five , TiCl_Four ・ C_Four H_Four O and the like. this
Among these titanium compounds, preferred is TiCl
_Four , Ti (OC₂ H _Five )_Four , Ti (OC_Four H₉ )_Four , T
i (OC_Four H₉ ) Cl₃ Etc.

The halogen source is usually supplied from the above-mentioned halogen compounds of magnesium and / or titanium, but known halogenating agents such as aluminum halides, silicon halides and phosphorus halides. It can also be supplied from The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid components used in the present invention are the above-mentioned essential components.
Other than SiCl_Four , CH₃ SiCl ₃ Silicon compounds such as
Substances, polymers such as methyl hydrogen polysiloxane
Silicon compound, Al (OiC₃ H₇ )₃ , AlCl₃ ,
AlBr₃ , Al (OC₂ H_Five)₃ , Al (OCH₃ )₂
 Aluminum compounds such as Cl and B (OCH₃ )₃ ,
B (OC₂ H_Five )₃ , B (OC₆ H_Five )₃ Boration of etc.
Compound, WCl₆ , MoCl_Five It is possible to use other ingredients such as
Yes, these are composed of silicon, aluminum, boron, etc.
It does not matter that the solid component remains in the solid component. Change
In addition, when manufacturing this solid component,
It can also be used as a donor and manufactured.

Examples of electron donors (internal donors) that can be used for the production of this solid component are alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers and diethers. Examples thereof include oxygen-containing electron donors such as acid amides and acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol, (b) phenol, cresol, xylenol, ethylphenol,
Propylphenol, cumylphenol, nonylphenol, naphthol and other C6 to C25 phenols, which may have an alkyl group, (C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other C3 to C15 phenols Ketones, (d) acetaldehyde, propionaldehyde,
C2-C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (e) formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, propionic acid ethyl,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
Diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate and the like having 2 to 2 carbon atoms
0 organic acid esters, (f) ethyl silicate, butyl silicate, inorganic acid esters such as silicates such as phenyltriethoxysilane, (to) acetyl chloride, benzoyl chloride, toluyl chloride, anisic acid Acid halides having 2 to 15 carbon atoms such as chloride, phthaloyl chloride and isophthaloyl chloride, and 2 to 2 carbon atoms such as (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.
0 ethers, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-
Diethers such as sec-butyl-1,3-dimethoxypropane, acid amides such as (li) acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine,
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Examples thereof include amines such as picoline and tetramethylethylenediamine, and nitriles such as (l) acetonitrile, benzonitrile and tolunitrile. Two or more kinds of these electron donors can be used. Among these, organic acid esters and organic acid halides and diethers are preferable, and phthalic acid esters, cellosolve acetate, phthalic acid halides and diethers are particularly preferable.

The amounts of the above-mentioned components used may be arbitrary as long as the effects of the present invention are recognized, but in general,
The following range is preferable. The amount of titanium compound used is 1 × in molar ratio with respect to the amount of magnesium compound used.
It is preferably in the range of 10 ^{−4 to} 1000, and preferably 0.01.
Within the range of 10 to 10. When a compound therefor is used as a halogen source, the amount used is 1 × 10 6 in molar ratio with respect to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen. ^{-2 to} 1000, preferably 0.
It is within the range of 1 to 100.

The amount of silicon, aluminum and boron compounds used is 1 × 10 ^{−3 to} 100, preferably 0.01 to 10 in molar ratio with respect to the amount of the above magnesium compound used.
It is within the range of 1. The amount of the electron-donating compound used is 1 × in molar ratio with respect to the amount of the above-mentioned magnesium compound used.
It is within the range of 10 ⁻³ to 10, preferably 0.01 to 5.

The solid component for producing component (A) is
It is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source and, if necessary, other components such as an electron donor. (A) A method in which a magnesium halide is optionally contacted with an electron donor and a titanium-containing compound. (B) A method of treating alumina or magnesia with a phosphorus halide compound, and bringing it into contact with a magnesium halide, an electron donor, and a titanium halogen-containing compound. (C) A titanium halogen compound and / or a silicon halogen compound, and optionally an electron donor, are contacted with a solid component obtained by contacting a magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound. Method. As the polymer silicon compound, those represented by the following formula are suitable.

[0027]

[Chemical 1]

(Here, R ² is a hydrocarbon residue having about 1 to 10 carbon atoms, and r is the viscosity of the polymer silicon compound.
The degree of polymerization is about 100 centistokes.) Of these, methylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-penta Methylcyclopentasiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane and the like are preferable.

(D) A method in which a magnesium compound is dissolved in titanium tetraalkoxide and an electron donor, and a titanium compound is brought into contact with a solid component precipitated by a halogenating agent or a titanium halogen compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact therewith as necessary. (F) A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxymagnesium compound in the presence or absence of an electron donor.

The production conditions for the component (A) of the present invention are:
The following range is preferable. The contact temperature is -50 to 200.
C., preferably 0 to 100.degree. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium agitating pulverizer and the like, and a method of agitating in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The component (A) used in the present invention can also be used as it has been subjected to a prepolymerization step of contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound or a styrene. . Specific examples of the olefins used in the prepolymerization include:
For example, those having about 2 to 20 carbon atoms, specifically ethylene, propylene, 1-butene, 3-methylbutene-1,
1-pentene, 1-hexene, 4-methylpentene-
1,1-octene, 1-decene, 1-undecene, 1-
There are eicosene and the like, and specific examples of the diene compound include
1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene,
1,4-pentadiene, 2,4-pentadiene, 2,6
-Octadiene, cis-2, trans-4-hexadiene, trans-2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene,
1,5-heptadiene, 1,6-heptadiene, 2,4
-Heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- There are hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. Further, specific examples of styrenes include styrene,
Examples include α-methylstyrene, allylbenzene and chlorostyrene.

The reaction conditions of the titanium component and the above vinyl group-containing compound may be arbitrary as long as the effects of the present invention are recognized, but generally, the following range is preferable. The prepolymerization amount of the vinyl group-containing compound is 0.001 to 1000 g, preferably 1 per gram of titanium solid component.
It is in the range of ˜100 grams, more preferably 5 to 50 grams. The reaction temperature during prepolymerization is -150 to 85.
C., preferably 0 to 50.degree. Then, a "main polymerization", that is, a polymerization temperature lower than the polymerization temperature at the time of the polymerization of the α-olefin is preferable. The reaction is generally preferably carried out under stirring, at which time n-hexane, n-
An inert solvent such as heptane may be present, the vinyl compound itself may be used as a medium, or depending on the type of the vinyl compound, the reaction may be performed in a gas phase. Further, two or more kinds of this vinyl group-containing compound can be used in combination. Further, the melting point of the prepolymerized polymer is preferably 200 ° C. or higher for the reason of improving the activity of the component (A).

<Component (B)> The component (B) of the present invention is an organoaluminum compound represented by the following general formula [I],
Alternatively, a mixture of an organoaluminum compound represented by the following general formula [II] and an organoaluminum compound represented by the following general formula [III], AIR ³ _3-n X ¹ _n [I] (wherein R ³ is It is a hydrocarbon residue having 1 to 20 carbon atoms, X ¹ is halogen or hydrogen, and n is 0 ≦ n ≦ 1.
AIR ⁴ _3-m X ² _m [II] (wherein R ⁴ is a hydrocarbon residue having 1 to 20 carbon atoms, X ² is halogen or hydrogen, and m is 0 ≦ m. ≤3
AIR ⁵ _3-p (OR ⁶ ) _p [III] (wherein R ⁵ is a hydrocarbon residue having 1 to 20 carbon atoms, R ⁶ is the same or different from R ³ and has 1 carbon atom). Is a hydrocarbon residue of 20 and p is a number of 0 <p <3).

Specific examples of the organoaluminum compound represented by the general formula [I] include (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum. , (B) Alkyl aluminum halides such as diethylaluminum monochloride and diisobutylaluminum monochloride, and (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Organoaluminium represented by the general formula [II]
Examples of the aluminum compound include Al (CH₃ )₃ , Al
(C₂ H_Five )₃ , Al (iC_Four H₉ )₃ , Al (C_Four H
₉ )₃, Al (n-C₆ H₁₃)₃ , Al (n-C₈ 
H₁₇)₃ , Al (C_TenH_{twenty one})₃ , (CH₃ )₂ AlC
l, (C₂ H_Five )₂ AlCl, (C₂ H_Five )₃ Al₂ C
l₃ , (C₂ H_Five ) AlCl₂ , (N-C₃ H₇ )₂ A
lCl, (i-C₃ H₇ )₂ AlCl, (n-C_Four H
₉ )₂ AlCl, (i-C_Four H₉ ) AlCl₂ , (N-
C ₆ H₁₃)₂ AlCl, (n-C₈ H₁₇)₂ AlCl,
(N-C_TenH_{twenty one})₂ AlCl and (C₂ H_Five )₂ Al
Br, etc.

Organoaluminium represented by the general formula [III]
Specific examples of the um compound include (CH₃ )₂ Al (OC
₂ H_Five ), (C₂ H_Five )₂ Al (OCH₃ ), (C₂ H
_Five ) ₂ Al (OC₂ H_Five ), (I-C₃ H₇ )₂ Al
(OC₂ H_Five ), (N-C₃ H ₇ )₂ Al (OCH
₃ ), (N-C_Four H₉ )₂ Al (OC₂ H_Five ), (N-
C₆H₁₃)₂ Al (OC_Four H₉ ), (N-C₈ H₁₇)₂ 
Al (OCH₃ ), (N-C _TenH_{twenty one})₂ Al (OC₂ H
_Five ), (CH₃ ) Al (OCH₃ )₂ , (C₂ H_Five ) A
l (OC₂ H_Five )₂ , (I-C₃ H₇ ) Al (OC_Four H
₉ )₂ , (N-C_Four H ₉ ) Al (OC₆ H_Five )₂ , (N
-C₆ H₁₃) Al (OC₆ H₁₃)₂ And (n-C_TenH
_{twenty one}) Al (OCH₃ )₂ Etc.

When a mixture of the organoaluminum compound of the general formula [II] and the organoaluminum compound of the general formula [III] is used as the component (B), their mixing ratio is
The molar ratio of the latter to the former is in the range of 0.1 to 100, preferably 0.1 to 10. The amount of component (B) used is (A
1 / Ti) is in the range of 0.1 to 1000, preferably 1 to 200.

<Component (C)> In the present invention, an electron donor can be used as the component (C), and specifically, specifically, organic acid or inorganic acid esters, diethers, ethers and amines can be used. It is possible to use one selected from the class.

The organic acid esters have 1 to 2 carbon atoms.
0 to 1 to 2 basic carboxylic acid or carbonic acid (in the present invention,
A typical example is an ester (including an intramolecular ester) of a C1 to C20 monohydric alcohol (including an ether alcohol) of carbonic acid treated as an organic acid). Specifically, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate. , Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, Methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone α- valerolactone, coumarin, phthalide, such as ethylene carbonate and the like.

Examples of the inorganic acid ester include esters of oxygen acids such as silicon, boron, phosphorus and aluminum with alcohols as described above for organic acid esters. A part of the valence of these elements may be satisfied by a hydrocarbon residue (having about 1 to 8 carbon atoms) or a halogen atom. Among such inorganic acid esters, esters of silicon oxyacids are preferred.

As a concrete example, (CH₃ ) Si (OCH
₃ )₃ , (CH₃ ) Si (OC₂ H_Five)₃ , (C₂ H
_Five )₂ Si (OCH₃ )₂ , (N-C₆ H₁₃) Si (O
CH₃ ) ₃ , (C₂ H_Five ) Si (OC₂ H_Five )₃ , (N
-C_TenH_{twenty one}) Si (OC₂ H_Five ) ₃ , (CH₂ = CH)
Si (OCH₃ )₃ , Cl (CH₂ )₃ Si (OCH
₃ ) ₃ , Si (OCH₃ )_Four , Si (OC₂ H_Five )₃ C
l, (C₂ H_Five )₂ Si (OC₂ H_Five )₂ , (C
₁₇H₃₅) Si (OCH₃ )₃ , Si (OC₂ H_Five )_Four ,
(C ₆ H_Five ) Si (OCH₃ )₃ , Si (OCH₃ )₂ 
Cl₂ , (C₆ H_Five )₂ Si (OCH₃ )₂ , (C₆ H
_Five ) (CH₃ ) Si (OCH₃ )₂ , (C₆ H_Five ) Si
(OC₂ H_Five )₃ , (I-C₃ H₇ )₂ Si (OCH
₃ )₂ , (I-C₃ H₇) Si (OC₂ H_Five )₃ , (I
-C_Four H₉ )₂ Si (OCH₃ )₂ , (C₆ H₁₁)₂ S
i (OCH₃ )₂ , (C₆ H₁₁) (CH₃ ) Si (OC
H₃ )₂ , (C_FiveH_Five ) Si (OCH₃ )₂ , (C₆ H_Five
 )₂ Si (OC₂ H_Five )₂ , (C₆ H_Five) (CH₃ ) S
i (OC₂ H_Five )₂ , (N-C₃ H₇ ) Si (OC₂ H
_Five )₃ , (CH₃ ) Si (OC₃ H₇ )₃ , (C₆ 
H_Five) (CH₂) Si (OC₂H_Five)₃ ,

[0042]

[Chemical 2]

(CH₃ )₃ CSi (CH₃ ) (OCH
₃ )₂ , (CH₃ )₃ CSi (HC (CH₃ )₂ ) (O
CH₃ )₂ , (CH₃ )₃ CSi (CH₃) (OC₂ H_Five
 )₂, (CH₃ )₃ CSi (C₂ H_Five ) (OCH₃ )
₂ , (C₂ H_Five )₃ CSi (CH₃ ) (OCH₃ )₂ ,
(CH₃ )₃ CSi (n-C₃ H₈ ) (OCH₃ )₂ ,
(CH₃ ) (C₂ H_Five ) CH-Si (CH₃ ) (OCH
₃ )₂ , (CH₃ ), CSi (sec-C₃ H₈ ) (O
CH₃ )₃ , ((CH₃ )₂ CHCH₂ ) Si (OCH
₃ )₂ , (CH₃ )₃ CSi (i-C₃H₈ ) (OCH₃
 )₂ , C₂ H_FiveC (CH₃ )₂ Si (CH₃ ) (OCH
₃ )₂ , (CH₃ )₃ CSi (n-C_FourH₉ ) (OCH₃
 )₂ , C₂H_FiveC (CH₃)₂ Si (CH₃ ) (OC₂ H
_Five )₂, (CH₃ )₃ CSi (OCH₃ )₃ , (CH
₃ )₃ CSi (OC₂ H_Five )₃ , (C₂ H_Five )₃ CSi
(OC₂ H_Five )₃ , (CH₃ )₃ CSi (i-C_Four H
₉ ) (OCH₃ )₂ , (CH₃ ) (C₂H_Five) CHSi
(OCH₃ )₃ , (CH₃ )₃CSi (sec-C_Four H₉
 ) (OCH₃ )₂ , (I-C₃ H₇ )₂ Si (OCH ₃
 )₂ , (C₆ H₁₁) (CH₃ ) Si (OCH₃ )₂ ,
(CH₃ )₃ CSi (n-C₆ H₁₃) (OCH₃ )₂ ,
(C₆ H₁₁)₂ Si (OCH₃ )₂ , (CH₃ ) ₃ CS
i (C₆ H₁₁) (OCH₃ )₂ , (I-C₃ H₇ )₂ S
i (OC₂ H_Five ) ₂ , ((CH₃ )₃ C)₂ Si (OC
H₃ )₂ , (CH₃ )₃ CSi (C_Five H_Five) (OCH
₃ )₂ , (I-C_Four H₉ )₂ Si (OCH₃ )₂ , HC
(CH₃ )₂C (CH₃ )₂ Si (CH₃ ) (OCH
₃ )₂ , (C₆ H₁₁) (CH₃ ) Si (OC₂ H_Five )
₂ , HC (CH₃ )₂ C (CH₃ )₂ Si (OCH₃ )
₃ , (C_FiveH_Five )₂ Si (OCH₃ )₂ , (I-C₃ H₇
 ) Si (OCH₃ )₃ Etc. Among these
Preferably, the α-position carbon is secondary or tertiary and has 3 carbon atoms.
-20, and particularly preferably the carbon at the α-position is tertiary and has 4 to 4 carbon atoms.
12, a silicon compound having a branched hydrocarbon residue
is there. Here, “branched chain” means branched aliphatic and cyclic
Including aliphatic.

So-called "hindered amines" are suitable as amines. In particular, 2,2,5,5- (in the case of pyrrolidine) or 2,2,6,6-tetra-lower alkyl of N-substituted (substituent is a lower alkyl group or lower alkylaluminum group) or unsubstituted pyrrolidine or piperidine Substitutes are typical. The following can be illustrated as such amines.

[0045]

[Chemical 3]

[0046]

[Chemical 4]

Suitable ethers are those which can be called hindered ethers. Particularly, those having at least two lower alkoxy groups on one carbon atom, and the carbon atom further having at least one 6-membered ring substituent are typical. The following can be illustrated as such ethers.

[0048]

[Chemical 5]

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

In the present invention, a diether compound may be used as the component (C). There is no limitation as long as it is a diether compound, but a diether compound having a branched aliphatic hydrocarbon and / or a cycloaliphatic hydrocarbon group is particularly preferable. Of these, 1,3-diethers are preferably used, and particularly 2,2-diisobutyl-1,3
-Dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2 , 2-diisopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-
1,3-dimethoxypropane, 2-cyclopentyl-2
-S-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3
-Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2
-Isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl- 1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-
1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,
3-dimethoxypropane is preferably used. When the component (C) is used, the amount used is in the range of 0.01 to 100 in terms of molar ratio to the component (B), preferably 0.1.
Within the range of 10 to 10.

<Catalyst Formation> The catalyst according to the present invention comprises components (A) and (B) or components (A), (B) and (C). According to the above, the fourth component is stirred in the polymerization tank or in the coexistence of an olefin to be polymerized, or outside the polymerization tank or in the presence of an olefin to be polymerized, at a time, stepwise or divided for several times. Can be formed by bringing them into contact with each other.

The method of supplying the components (A), (B) and (C) to the contacting place is not particularly limited, but they are dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane and polymerized separately. It is usually added to the tank. The component (A) may be added to the polymerization tank in a solid state separately from the component (B) or the component (C).

[0055]

EXAMPLES In the following examples, the differential thermal analysis (DSC measurement) for measuring the melting point was performed by DSC manufactured by Perkin Elmer Co.
Performed using type 2. Example 1 [Production of Component (A)] In a flask thoroughly replaced with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 10 g of Mg (OEt) ₂ was introduced to make a suspension state. Then, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 1.9 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was introduced, and the temperature was raised to 110 ° C. to react for 3 hours. It was
After completion of the reaction, it was washed with toluene. Then TiCl ₄ 2
0 ml and 100 ml of toluene were introduced and the reaction was carried out at 110 ° C for 2 hours. After completion of the reaction, n-
It was thoroughly washed with heptane to obtain a solid component (A-1) for producing the component (A). The titanium content of this product was 2.5% by weight.

Then, 200 ml of n-heptane purified in the same manner as above was introduced into an autoclave sufficiently replaced with nitrogen, 5 g of the solid component synthesized above was introduced, and then 1.5 g of triethylaluminum was introduced. Prepolymerization of 4-methylpentene-1 was carried out at 20 ° C. After the completion of the prepolymerization, it was thoroughly washed with n-heptane to obtain a component (A). A portion was taken out and examined for the amount of prepolymerization. 10.6 g Poly 4-methylpentene-
It was 1 / gram solid component (A-1). In addition, poly 4-
The melting point of methylpentene-1 was 231 ° C.

[Polymerization of Propylene] 100 ml of sufficiently dehydrated and deoxygenated propylene was added to a stainless steel autoclave having an internal volume of 1.0 liter equipped with a stirring and temperature control device, and 25 ml of triethylaluminum 8 was added as component (B). .9 milligram was introduced. While introducing propylene into the autoclave, raise the temperature and pressure to 1
The reaction system was brought to a supercritical state at 80 ° C. and 100 kg / cm ² . Then, the component (A) produced above is added to the component (A-
1) Introducing 10 milligrams on the basis of the standard, starting the polymerization and conducting the polymerization for 45 minutes. After the polymerization was completed, 15 ml of ethanol was added to stop the reaction. 104 g of polymer were obtained, MFR = 51.8 g / 10 min, I.V. by boiling n-heptane extraction. It was I = 95.3 wt%. The Q value was 6.2.

Example 2 [Production of Component (A)] In a flask thoroughly replaced with nitrogen,
Introduce 200 ml of dehydrated and deoxygenated n-heptane, then 0.4 mol of MgCl ₂ , Ti (O 2
-NC ₄ H _{9) 4} was 0.8 mol introduced and reacted for 2 hours at 95 ° C.. After the reaction was completed, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours.
The solid component produced was washed with n-heptane.

Then, in a flask that had been sufficiently replaced with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced, and the solid component synthesized above was converted into Mg atom in terms of Mg.
24 mol was introduced. Next, 0.4 ml of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane. Then, 25 ml of n-heptane was mixed with 0.024 mol of phthalic acid chloride and introduced into the flask at 70 ° C. for 30 minutes.
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, it was washed with n-heptane. After completion of the reaction, it was washed with n-heptane. Then, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, the solid component (A-) for producing the component (A) is thoroughly washed with n-heptane.
1). The titanium content of this product was 2.6% by weight.

Then, 200 ml of n-heptane purified in the same manner as above was introduced into an autoclave sufficiently replaced with nitrogen, 5 g of the solid component synthesized above was introduced, and then 1.5 g of triethylaluminum was introduced. Preliminary polymerization of 3-methylbutene-1 was carried out at 10 ° C. After the completion of the prepolymerization, it was thoroughly washed with n-heptane to obtain a component (A). A portion was taken out and examined for the amount of prepolymerization. 12.7 g Poly-3-methylbutene-1 /
It was a gram solid component (A-1). The melting point of poly-3-methylbutene-1 was 302 ° C.

[Polymerization of Propylene] Propylene was introduced into the autoclave in the same manner as in Example-1. Then, 4.7 mg of triethylaluminum as the component (B) and (CH ₃ ) ₃ CSi (n-C ₃ H ₇ ) as the component (C).
) (OCH ₃ ) ₂ 1.0 mg, then hydrogen 5
Introduced milliliters. While introducing propylene into the autoclave, the temperature is raised and the pressure is increased to 200 ° C and 150 kg / c.
The reaction system was brought to a supercritical state at m ² . Then, 3 mg of the component (A) produced above was introduced on the basis of the component (A-1) to start the polymerization, and the polymerization was continued for 45 minutes to terminate the reaction in the same manner as in Example-1. 127 grams of polymer are obtained,
MFR = 68.2 g / 10 min, I.V. by boiling n-heptane extraction. It was I = 97.1 wt%. The Q value was 7.1.

Examples 3 to 6 Using the component (A) prepared in Example-2, the components (B) and (C) shown in Table 1 were used to obtain the polymerization conditions shown in Table 1. Polymerization was carried out under the same conditions as in Example 2 except for the above. The results are shown in Table 1.

[0063]

[Table 1]

[Brief description of drawings]

FIG. 1 is a flow chart for facilitating the understanding of the present invention.

─────────────────────────────────────────────────── --- Continuation of front page (56) References JP-A-64-69610 (JP, A) JP-A-7-316220 (JP, A) JP-A-7-179514 (JP, A) JP-A-8- 231625 (JP, A) JP-A-9-52911 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 2/00-2/60, 4/654

Claims (8)

(57) [Claims] 1. A comonomer other than propylene,
Ethylene or an α-olefin having 4 to 12 carbon atoms
A method for polymerizing a propylene-based monomer , which may comprise 0.01 to 30% by weight , wherein the polymerization temperature is higher than the critical temperature of the monomer component present in the polymerization system and The temperature is not lower than the melting point, the polymerization pressure is higher than the critical pressure of the monomer components present in the polymerization system, and the polymerization temperature is 170.
° C. to 250 DEG ° C., the polymerization pressure is 50~300kg / cm ²
The method for polymerizing propylene, characterized in that propylene is subjected to solventless polymerization under the condition of being within the range . 2. The Q value of the polymer is 6 or more.
The propylene polymerization method described. 3. The method for polymerizing propylene according to claim 1, wherein a Ziegler type catalyst is used. 4. The method for polymerizing propylene according to claim 1, wherein a magnesium-supported catalyst is used. 5. The method for polymerizing propylene according to claim 1, wherein a catalyst prepolymerized with a vinyl group-containing compound is used. 6. The melting point of the prepolymerized polymer is 200 ° C.
The propylene polymerization method according to claim 5, which is the above. 7. A propylene-based polymer, which is a polymer polymerized by the method according to claim 1, wherein the MFR of the polymer is 5 to 1000 g / 10 minutes. 8. A propylene-based polymer, which is a polymer polymerized by the method according to claim 1, wherein the Q value of the polymer is 6 or more.